(2Z,4E,8E,12E)-2-(1-Methylethyl)-5,9,13-trimethyl-2,4,8,12-tetradecatetraenenitrile | 130675-18-2

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (2Z,4E,8E,12E)-2-(1-Methylethyl)-5,9,13-trimethyl-2,4,8,12-tetradecatetraenenitrile
• 英文别名: (2Z,4E,8E)-5,9,13-trimethyl-2-propan-2-yltetradeca-2,4,8,12-tetraenenitrile
• CAS: 130675-18-2
• 化学式: C₂₀H₃₁N
• 分子量: 285.473
• InChiKey: AQROFDJIBGKDOT-PNLWUKOVSA-N

物化性质

• 沸点：
  413.8±24.0 °C(Predicted)
• 密度：
  0.875±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.9
• 重原子数：
  21
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  23.8
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (2Z,4E,8E,12E)-2-(1-Methylethyl)-5,9,13-trimethyl-2,4,8,12-tetradecatetraenenitrile 在 potassium cyanide 、 18-冠醚-6 叔丁基过氧化氢 、 四氯化碳 、 selenium(IV) oxide 、 二异丁基氢化铝 、 三苯基膦 、 水杨酸 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 甲苯 为溶剂， 反应 34.33h， 生成 (2Z,4E,8E,12E)-2-(1-Methylethyl)-5,9,13-trimethyl-2,4,8,12-cyclotetradecatetraen-1-one
  参考文献：
  名称：

  Total Synthesis of Sarcophytol A, an Anticarcinogenic Marine Cembranoid

  摘要：

  A highly stereo- and enantioselective total synthesis of sarcophytol A (1), a marine cembranoid promising as a cancer chemopreventive agent, is described. The nitrile 10 obtained Z-selectively (Z:E = >35:1) by the Horner-Emmons reaction of (E,E)-farnesal (5) with the phosphononitrile 9 in 91% yield was converted to the conjugated 2(Z),4(E)-dienal 3 in which the terminal (E)-methyl group was functionalized. Intramolecular alkylation of the cyanohydrin TMS ether of 3 provided the macrocyclic ketone 2 in 79% of overall yield from 3 without isolation of the cyclic cyanohydrin 20 as well as its TMS ether 19. Reduction of 2 with several chiral LiAlH4 reagents afforded 1 highly enantioselectively (87-93% ee) in 78-97% yield, from which enantiomerically pure 1 (>99% ee) was readily obtained upon a single recrystallization.

  DOI：

  10.1021/jo00089a011
• 作为产物：
  描述：

  Farnesal 以96%的产率得到
  参考文献：
  名称：

  TAKAYANAGI, HISAO;KITANO, YASUNORI;MORINAKA, YASUHIRO, TETRAHEDRON LETT., 31,(1990) N3, C. 3317-3320

  摘要：

  DOI：

文献信息

• Z-selective formation of trisubstituted α,β-unsaturated nitrile by the Horner-Emmons reaction
  作者：Hisao Takayanagi

  DOI：10.1016/s0040-4039(00)76763-3

  日期：1994.3

  Conditions which allow the Horner-Emmons reaction of phosphononitrile to proceed Z-selectively were clarified. The generality and usefulness of the procedure were demonstrated by an application to a stereoselective synthesis of plaunotol (9).

  明确了允许磷腈的霍纳-埃蒙斯反应进行Z选择性的条件。该方法的普遍性和实用性通过在立体选择性合成青草醇中的应用得到了证明（9）。
• TAKAYANAGI, HISAO;KITANO, YASUNORI;MORINAKA, YASUHIRO, TETRAHEDRON LETT., 31,(1990) N3, C. 3317-3320
  作者：TAKAYANAGI, HISAO、KITANO, YASUNORI、MORINAKA, YASUHIRO

  DOI：——

  日期：——
• Total Synthesis of Sarcophytol A, an Anticarcinogenic Marine Cembranoid
  作者：Hisao Takayanagi、Yasunori Kitano、Yasuhiro Morinaka

  DOI：10.1021/jo00089a011

  日期：1994.5

  A highly stereo- and enantioselective total synthesis of sarcophytol A (1), a marine cembranoid promising as a cancer chemopreventive agent, is described. The nitrile 10 obtained Z-selectively (Z:E = >35:1) by the Horner-Emmons reaction of (E,E)-farnesal (5) with the phosphononitrile 9 in 91% yield was converted to the conjugated 2(Z),4(E)-dienal 3 in which the terminal (E)-methyl group was functionalized. Intramolecular alkylation of the cyanohydrin TMS ether of 3 provided the macrocyclic ketone 2 in 79% of overall yield from 3 without isolation of the cyclic cyanohydrin 20 as well as its TMS ether 19. Reduction of 2 with several chiral LiAlH4 reagents afforded 1 highly enantioselectively (87-93% ee) in 78-97% yield, from which enantiomerically pure 1 (>99% ee) was readily obtained upon a single recrystallization.